CN114867703A

CN114867703A - Fluorene-based compound, organic light emitting device using the same, and method of manufacturing the same

Info

Publication number: CN114867703A
Application number: CN202180007078.4A
Authority: CN
Inventors: 金志勋; 裴在顺; 李载澈; 崔斗焕; 姜成京; 郑珉硕
Original assignee: LG Chem Ltd
Current assignee: LG Chem Ltd
Priority date: 2020-01-08
Filing date: 2021-01-06
Publication date: 2022-08-05
Anticipated expiration: 2041-01-06
Also published as: KR20210089587A; JP2023505978A; US20230098935A1; JP7403912B2; CN114867703B; EP4063342A4; EP4063342A1; WO2021141382A1

Abstract

The present specification relates to a fluorene-based compound of chemical formula 1, a coating composition including the fluorene-based compound of chemical formula 1, an organic light emitting device using the same, and a method of manufacturing the same.

Description

Fluorene-based compound, organic light emitting device using the same, and method of manufacturing the same

Technical Field

This application claims priority and benefit from korean patent application No. 10-2020-.

The present specification relates to a fluorene-based compound, a coating composition including the fluorene-based compound, an organic light emitting device formed by using the coating composition, and a method of manufacturing the same.

Background

The organic light emitting phenomenon is one of examples of converting a current into visible light by an internal process of a specific organic molecule. The principle of the organic light emitting phenomenon is as follows. When an organic material layer is provided between an anode and a cathode and a current is applied between the two electrodes, electrons and holes are injected from the cathode and the anode into the organic material layer, respectively. The electrons and holes injected into the organic material layer are recombined to form excitons, and the excitons fall back to the ground state again to emit light. An organic light emitting device using this principle may be generally composed of a cathode, an anode, and organic material layers (for example, organic material layers including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer) disposed therebetween.

Materials used in the organic light emitting device are mainly pure organic materials or complex compounds in which organic materials and metals form complexes, and may be classified into hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, and the like according to their uses. Here, an organic material having p-type characteristics (i.e., an organic material that is easily oxidized and electrochemically stable when the material is oxidized) is generally used as the hole injection material or the hole transport material. Meanwhile, an organic material having n-type characteristics (i.e., an organic material that is easily reduced and electrochemically stable when the material is reduced) is generally used as an electron injecting material or an electron transporting material. As the light emitting layer material, a material having both p-type characteristics and n-type characteristics (i.e., a material that is stable in both an oxidized state and a reduced state) is preferable, and when an exciton is formed, a material having high light emitting efficiency to convert the exciton into light is preferable.

In order to obtain a high-efficiency organic light-emitting device capable of being driven at a low voltage, it is necessary to smoothly transfer holes or electrons injected into the organic light-emitting device to the light-emitting layer, and at the same time, to prevent the injected holes and electrons from being released from the light-emitting layer. For this purpose, materials used in organic light emitting devices need to have appropriate band gaps and HOMO or LUMO energy levels.

In addition, materials used in organic light emitting devices are required to have excellent chemical stability, excellent charge mobility, excellent interfacial characteristics with electrodes or adjacent layers, and the like. That is, the material used in the organic light emitting device needs to be minimally deformed by moisture or oxygen. In addition, the material used in the organic light emitting device needs to have appropriate hole or electron mobility to balance the density of holes and electrons in the light emitting layer of the organic light emitting device, thereby forming excitons to the maximum extent. In addition, materials used in organic light emitting devices need to improve an interface with an electrode containing a metal or metal oxide for stability of the device.

In addition to those described above, the materials used in the organic light emitting device for the solution method are required to additionally have the following characteristics.

First, materials used in organic light emitting devices need to form storable homogeneous solutions. Since commercial materials used for the deposition method have good crystallinity so that the materials cannot be well dissolved in a solution or easily form crystals even if the materials form a solution, it is highly likely that the concentration gradient of the solution changes with storage time or a defective device is formed.

Second, a layer in which a solution process is performed needs to have resistance to a solvent and a material used during a process of forming other layers, and to have excellent current efficiency and excellent life characteristics when manufacturing an organic light emitting device.

Therefore, there is a need in the art to develop new organic materials.

Disclosure of Invention

Technical problem

The present specification provides a fluorene-based compound that can be used in an organic light emitting device for a solution process and an organic light emitting device including the same.

Technical scheme

An exemplary embodiment of the present specification provides a fluorene-based compound represented by the following chemical formula 1.

[ chemical formula 1]

In the chemical formula 1, the first and second,

r1 to R6 are the same or different from each other and are each independently hydrogen; deuterium; a halogen group; substituted or unsubstituted alkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group,

l1 and L2 are the same or different from each other and are each independently a direct bond; or a substituted or unsubstituted alkylene group,

ar1 and Ar2 are the same or different from each other and are each independently substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group,

x1 and X2 are the same or different from each other and are each independently a hydrogen or halogen group, and at least one of X1 and X2 is a halogen group,

x3 and X4 are the same or different from each other and are each independently deuterium; substituted or unsubstituted alkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl; or a photo-curable group or a thermosetting group,

m1 and m2 are each an integer of 1 to 4,

n1 and n6 are each independently an integer from 0 to 5,

n2 and n5 are each independently an integer from 0 to 4,

n3 and n4 are each independently an integer of 0 to 3, an

When m1, m2, and n1 to n6 are each 2 or more, the substituents in parentheses are the same as or different from each other.

Further, an exemplary embodiment of the present specification provides a coating composition including the fluorene-based compound.

Further, an exemplary embodiment of the present specification provides an organic light emitting device including: a first electrode;

a second electrode; and

an organic material layer having one or more layers disposed between the first electrode and the second electrode,

wherein one or more of the organic material layers comprise the coating composition or a cured product thereof, and

the cured product of the coating composition is in a state in which the coating composition is cured by heat treatment or light treatment.

Further, an exemplary embodiment of the present specification provides a method for manufacturing an organic light emitting device, the method including: preparing a substrate;

forming a first electrode on a substrate;

forming an organic material layer having one or more layers on the first electrode; and

a second electrode is formed on the organic material layer,

wherein forming the organic material layer includes forming the organic material layer having one or more layers by using the coating composition.

Advantageous effects

A core structure of the fluorene-based compound according to one exemplary embodiment of the present specification is substituted with a halogen group. Accordingly, the fluorene-based compound according to one exemplary embodiment of the present specification has a relatively large dipole moment and a relatively low HOMO level, compared to a compound having a core structure that is not substituted with a halogen group. Accordingly, the fluorene-based compound according to one exemplary embodiment of the present specification exhibits long lifespan characteristics when applied to an organic light emitting device.

Further, the fluorene-based compound according to one exemplary embodiment of the present specification forms a stable thin film that is not damaged in a subsequent solution process by a heat treatment or UV treatment of 250 ℃ or less.

The thin film having the coating composition including the compound according to one exemplary embodiment of the present specification applied thereon is formed into a stable thin film that is not damaged in a subsequent solution process by a heat treatment of 250 ℃ or less or a UV treatment.

The fluorene-based compound according to one exemplary embodiment of the present specification may be used as a material of an organic material layer of an organic light emitting device for a solution process, and may provide low driving voltage, high light emitting efficiency, and high lifespan characteristics. In addition, since the fluorene-based compound is used, the solubility is improved, so that there are advantages in that: when the ink of the solution method is prepared, the selection of the solvent is widened, and the melting point and the curing temperature can be lowered.

Drawings

Fig. 1 illustrates an example of an organic light emitting device according to an exemplary embodiment of the present specification.

FIG. 2 is a graph showing the results of NMR measurement of intermediate A-1.

Fig. 3 is a graph showing HPLC measurement results of compound 1.

Fig. 4 is a graph showing the film retention experiment result of the thin film formed from the coating composition 1 prepared in experimental example 1.

Fig. 5 is a graph showing the film retention experiment result of the thin film formed from the coating composition 2 prepared in experimental example 1.

101: substrate

201: anode

301: hole injection layer

401: hole transport layer

501: luminescent layer

601: electron injection and transport layer

701: cathode electrode

Detailed Description

In general, since a single molecule based on arylamine used in an organic light emitting device for a solution method is not resistant to a solvent in a subsequent process, it is necessary to introduce a curing group into a single molecule of a compound based on arylamine that can be used in an organic light emitting device for a solution method.

A thin film manufactured by subjecting the coating composition comprising the fluorene compound bonded with an amine group according to the present invention to a heat treatment or a light treatment provides an organic light emitting device having excellent resistance to a solvent as well as excellent current efficiency and device characteristics.

Hereinafter, the present specification will be described in detail.

In this specification, when one member is disposed "on" another member, this includes not only a case where one member is in contact with another member but also a case where another member is present between the two members.

In the present specification, when a portion "includes" one constituent element, unless specifically described otherwise, this is not intended to exclude another constituent element, but is intended to mean that another constituent element may be further included.

[ chemical formula 1]

In the chemical formula 1, the first and second,

m1 and m2 are each an integer of 1 to 4,

n1 and n6 are each independently an integer from 0 to 5,

n2 and n5 are each independently an integer from 0 to 4,

n3 and n4 are each independently an integer of 0 to 3, an

In the present specification, at least one of X1 and X2 is a halogen group. That is, the core structure of the compound represented by chemical formula 1 is substituted with one or more halogen groups. Accordingly, the fluorene-based compound according to one exemplary embodiment of the present specification has a relatively large dipole moment and a relatively low HOMO level, compared to a compound having a core structure that is not substituted with a halogen group. Accordingly, the fluorene-based compound according to one exemplary embodiment of the present specification exhibits a long lifespan characteristic when applied to an organic light emitting device.

In the present specification, "thermosetting group or photocurable group" may mean a reactive substituent that crosslinks a compound when exposed to heat and/or light. When radicals generated by decomposing the carbon-carbon multiple bond and the cyclic structure by heat treatment or light irradiation are linked to each other, crosslinking may be generated.

In one exemplary embodiment of the present specification, the thermosetting group or the photocurable group is any one of the following structures.

In one exemplary embodiment of the present specification, the fluorene-based compound represented by chemical formula 1 may realize a large-area organic light emitting device and have economic benefits in terms of time and cost because the device may be manufactured by a solution application method.

Further, when the coating layer is formed by using the fluorene-based compound represented by chemical formula 1, the thermosetting group or the photocurable group is cross-linked by heat or light, so that when additional layers are stacked on the upper portion of the coating layer, it is possible to maintain the coating layer by preventing the fluorene-based compound contained in the coating composition from being washed away by the solvent and simultaneously stacking the additional layers on the upper portion.

In addition, in the fluorene-based compound represented by chemical formula 1, the thermosetting group or the photocurable group forms a crosslink to form a coating layer, so that there are effects that chemical resistance of the coating layer to a solvent is enhanced and film retention rate is high.

Further, the fluorene-based compound in which crosslinks are formed by heat treatment or light irradiation according to one exemplary embodiment of the present specification has an effect of being excellent in thermal stability because a plurality of fluorene-based compounds are crosslinked and thus provide crosslinks in the form of a thin film in an organic light emitting device.

Hydrogen or deuterium may be bonded to a position of the compound described in the present specification to which no substituent is bonded.

In the context of the present specification,

and

means a moiety bonded to another substituent or bonding moiety.

In the present specification, the term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent, and the position of substitution is not limited as long as the position is a position at which the hydrogen atom is substituted (i.e., a position at which the substituent may be substituted), and when two or more are substituted, two or more substituents may be the same as or different from each other.

In the present specification, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from: hydrogen; deuterium; a halogen group; a nitrile group; a nitro group; an alkyl group; an alkoxy group; an aryl group; and heteroaryl, or unsubstituted or substituted with a substituent linked to two or more of the substituents exemplified above. For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, biphenyl can also be aryl and can be interpreted as a substituent with two phenyl groups attached.

In the present specification, a halogen group is fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear, branched or cyclic, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms of the alkyl group is from 1 to 20. Specific examples thereof include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, pentyl group, n-pentyl group, isopentyl group, tert-pentyl group, hexyl group, n-hexyl group, heptyl group, n-heptyl group, hexyl group, n-hexyl group and the like, but are not limited thereto.

In the present specification, an alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20. Specific examples thereof include methoxy group, ethoxy group, n-propoxy group, isopropoxy group (isopropoxy group), isopropyloxy group (i-propyloxy group), n-butoxy group, isobutoxy group, t-butoxy group, sec-butoxy group, n-pentyloxy group, neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3-dimethylbutyloxy group, 2-ethylbutoxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, benzyloxy group, p-methylbenzyloxy group and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the number of carbon atoms of the aryl group is 6 to 40. According to an exemplary embodiment, the number of carbon atoms of the aryl group is 6 to 20. Examples of the monocyclic aryl group as the aryl group include, but are not limited to, phenyl, biphenyl, terphenyl, and the like. Examples of polycyclic aromatic groups include naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, perylene,

A phenyl group, a fluorenyl group, and the like, but are not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

When the fluorenyl group is substituted, the fluorenyl group can be

(spirofluorene),

And the like. However, the substituent is not limited thereto.

In the present specification, a heteroaryl group contains one or more atoms other than carbon (i.e., one or more heteroatoms), and in particular, the heteroatoms may include one or more atoms selected from O, N, Se, S, and the like. The number of carbon atoms thereof is not particularly limited, but is preferably 2 to 60. According to an exemplary embodiment, the number of carbon atoms of the heteroaryl group is from 2 to 40. According to an exemplary embodiment, the number of carbon atoms of the heteroaryl group is from 2 to 20. Heteroaryl groups may be monocyclic or polycyclic.Examples of heterocyclic groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, and the like,

Azolyl group,

Oxadiazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzobenzoxazinyl

Azolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, phenanthrolinyl, thiazolyl, isoquinoyl

Azolyl group,

Oxadiazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but is not limited thereto.

In the present specification, the alkylene group may be selected from the above-mentioned examples of alkyl groups, except that it is a divalent group.

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each is independently hydrogen; deuterium; a halogen group; substituted or unsubstituted alkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl.

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each is independently hydrogen; deuterium; a halogen group; substituted or unsubstituted alkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl.

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each is independently hydrogen; deuterium; a halogen group; substituted or unsubstituted alkyl having 1 to 40 carbon atoms; a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each is independently hydrogen; deuterium; a halogen group; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each is independently hydrogen; deuterium; a halogen group; substituted or unsubstituted methyl; substituted or unsubstituted ethyl; substituted or unsubstituted propyl; substituted or unsubstituted butyl; substituted or unsubstituted isobutyl; substituted or unsubstituted tert-butyl; substituted or unsubstituted pentyl; or a substituted or unsubstituted hexyl group.

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each is independently hydrogen; deuterium; a halogen group; methyl unsubstituted or substituted with a halogen group; ethyl unsubstituted or substituted with a halogen group; propyl unsubstituted or substituted with a halogen group; substituted or unsubstituted butyl; isobutyl which is unsubstituted or substituted by halogen groups; tert-butyl unsubstituted or substituted with a halogen group; pentyl unsubstituted or substituted by a halogen group; or hexyl, unsubstituted or substituted with halo groups.

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each is independently hydrogen; deuterium; fluorine; unsubstituted or fluoro-substituted methyl; an ethyl group; propyl; a butyl group; an isobutyl group; a tertiary butyl group; a pentyl group; or a hexyl group.

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each is independently hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each is independently hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms which is unsubstituted or substituted with a halogen group.

In an exemplary embodiment of the present specification, R1 to R6 are the same as or different from each other, and each is independently hydrogen; unsubstituted or fluoro-substituted methyl; or a tert-butyl group.

In one exemplary embodiment of the present description, R1 and R6 are hydrogen; unsubstituted or fluoro-substituted methyl; or a tert-butyl group.

In one exemplary embodiment of the present description, R2 to R5 are hydrogen.

In an exemplary embodiment of the present specification, n1 and n6 are each an integer of 0 to 2.

In one exemplary embodiment of the present specification, Ar1 and Ar2 are the same or different from each other and each independently is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, Ar1 and Ar2 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In yet another exemplary embodiment, Ar1 and Ar2 are the same or different from each other and are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

According to one exemplary embodiment of the present description, Ar1 and Ar2 are the same or different from each other and are each independently a substituted or unsubstituted phenyl group; substituted or unsubstituted biphenyl; substituted or unsubstituted naphthyl; substituted or unsubstituted fluorenyl.

In one exemplary embodiment of the present specification, Ar1 and Ar2 are the same or different from each other and are each independently phenyl unsubstituted or substituted with deuterium or alkyl; biphenyl unsubstituted or substituted with deuterium or alkyl; naphthyl unsubstituted or substituted with deuterium or alkyl; fluorenyl unsubstituted or substituted with deuterium or alkyl.

In another exemplary embodiment, Ar1 and Ar2 are the same or different from each other and are each independently phenyl; a biphenyl group; or naphthyl.

In one exemplary embodiment of the present specification, Ar1 and Ar2 may be any one of the following structures, but are not limited thereto, and the following structures may be additionally substituted.

In the structure of the device, the air inlet pipe is provided with a plurality of air outlets,

w is O, S, NRa, CRbRc or SiRdRe,

r31 to R41, Ra, Rb, Rc, Rd and Re are the same or different from each other and are each independently hydrogen; deuterium; a halogen group; substituted or unsubstituted alkyl; or a substituted or unsubstituted aryl group,

p1 is an integer from 0 to 7,

p2, p4 and p5 are each integers from 0 to 4,

p3 and p6 are each an integer of 0 to 5,

when each of p1 to p6 is 2 or more, the substituents in parentheses are the same as or different from each other, and

is a moiety bonded to chemical formula 1.

In an exemplary embodiment of the present specification, R31 to R41 are the same as or different from each other, and each is independently hydrogen; deuterium; a halogen group; substituted or unsubstituted alkyl having 1 to 30 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R31 to R41 are the same as or different from each other, and each is independently hydrogen; deuterium; a halogen group; substituted or unsubstituted alkyl having 1 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In another exemplary embodiment, R31 to R41 are the same or different from each other and are each independently hydrogen; deuterium; a halogen group; substituted or unsubstituted alkyl having 1 to 8 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.

In yet another exemplary embodiment, each of R31 through R41 is hydrogen.

In an exemplary embodiment of the present specification, W is O.

In an exemplary embodiment of the present specification, W is S.

In an exemplary embodiment of the present specification, W is CRbRc.

In an exemplary embodiment of the present description, W is SiRdRe.

In an exemplary embodiment of the present specification, Rb, Rc, Rd and Re are the same or different from each other and each independently hydrogen; deuterium; a halogen group; substituted or unsubstituted alkyl having 1 to 30 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, Rb, Rc, Rd and Re are the same or different from each other and each independently hydrogen; deuterium; a halogen group; substituted or unsubstituted alkyl having 1 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In an exemplary embodiment of the present specification, Rb, Rc, Rd and Re are the same or different from each other and each independently hydrogen; deuterium; a halogen group; substituted or unsubstituted alkyl having 1 to 8 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.

In an exemplary embodiment of the present specification, Rb, Rc, Rd and Re are the same or different from each other and each independently hydrogen; deuterium; substituted or unsubstituted methyl; substituted or unsubstituted ethyl; or a substituted or unsubstituted phenyl group.

In an exemplary embodiment of the present specification, Rb, Rc, Rd and Re are the same or different from each other and each independently hydrogen; deuterium; a methyl group; an ethyl group; or a phenyl group.

In an exemplary embodiment of the present specification, X1 and X2 are the same or different from each other and are each independently a hydrogen or halogen group, and at least one of X1 and X2 is a halogen group.

In an exemplary embodiment of the present specification, X1 is a halogen group and X2 is hydrogen.

In an exemplary embodiment of the present specification, X1 is fluorine and X2 is hydrogen.

In an exemplary embodiment of the present specification, X1 is hydrogen and X2 is a halogen group.

In an exemplary embodiment of the present specification, X1 is hydrogen and X2 is fluorine.

In an exemplary embodiment of the present specification, X1 and X2 are each fluorine.

When L1 is a direct bond, the carbon number 9 of fluorene is directly bonded to X3, and its specific structure is as follows.

When L2 is a direct bond, the carbon number 9 of fluorene is directly bonded to X4, and its specific structure is as follows.

In an exemplary embodiment of the present specification, X3 and X4 are the same as or different from each other, and each is independently a photocurable group or a thermosetting group.

When X3 and X4 are photocurable groups or thermosetting groups, there is an advantage that a solution method can be performed when the compounds are applied to an organic light-emitting device.

For example, in forming the organic material layer by using a compound, a plurality of fluorene-based compounds form crosslinks by heat treatment or light treatment, so that the organic material layer including a thin film structure can be provided. In addition, when additional layers are stacked on the surface of the formed organic material layer, the organic material layer can be prevented from being dissolved, morphologically affected, or decomposed by a solvent.

In one exemplary embodiment of the present specification, X3 and X4 are the same as or different from each other, and each is independently a photocurable group or a thermosetting group, and may have the following structure.

In an exemplary embodiment of the present specification, X3 and X4 are

In an exemplary embodiment of the present specification, m1 and m2 are each 1.

In an exemplary embodiment of the present specification, chemical formula 1 is represented by the following chemical formula 1-1.

[ chemical formula 1-1]

In chemical formula 1-1, X1 to X4, L1, L2, R1 to R6, Ar1, Ar2, and n1 to n6 are the same as those defined in chemical formula 1.

By specifying the positions of X1 and X2, the compound represented by chemical formula 1-1 can be easily polymerized.

In one exemplary embodiment of the present specification, the fluorene-based compound of chemical formula 1 may be represented by any one of the following structures.

The fluorene-based compound according to one exemplary embodiment of the present specification may be prepared by a preparation method that will be described below.

For example, for the fluorene-based compound of chemical formula 1, the core structure may be prepared by the following preparation method. In this case, the substituents may be bonded by a method known in the art, and the type and position of the substituent or the number of the substituents may be changed according to a technique known in the art.

< general production method of chemical formula 1 >

The substituents for the preparation method are the same as the definition of the substituents of chemical formula 1.

An exemplary embodiment of the present specification provides a coating composition including the fluorene-based compound described above.

In one exemplary embodiment of the present specification, a coating composition includes a fluorene-based compound and a solvent.

In one exemplary embodiment of the present description, the coating composition may be in a liquid phase. By "liquid phase" is meant that the composition is liquid at room temperature at atmospheric pressure.

In one exemplary embodiment of the present specification, the above fluorene-based compound has solubility to some solvents.

In one exemplary embodiment of the present description, the solvent may be, for example: chlorine-based solvents such as chloroform, dichloromethane, 1, 2-dichloroethane, 1, 2-trichloroethane, chlorobenzene, and o-dichlorobenzene; ether-based solvents, examplesSuch as tetrahydrofuran and di

An alkane; aromatic hydrocarbon-based solvents such as toluene, xylene, trimethylbenzene, and mesitylene; aliphatic hydrocarbon-based solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; ketone-based solvents such as acetone, methyl ethyl ketone, cyclohexanone, isophorone, tetralone, decalone, and acetylacetone; ester-based solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; polyhydric alcohols such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerol, and 1, 2-hexanediol, and derivatives thereof; alcohol-based solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; sulfoxide-based solvents, such as dimethyl sulfoxide; amide-based solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide; and tetralin, but the solvent is sufficient as long as the solvent can dissolve or disperse the fluorene derivative according to one exemplary embodiment of the present invention, and is not limited thereto.

In one exemplary embodiment of the present specification, the solvent may be used alone or as a mixture of two or more solvents.

In one exemplary embodiment of the present specification, as a result of measuring the fluorene-based compound of chemical formula 1 by a Differential Scanning Calorimeter (DSC), a temperature difference between an exothermic peak and an endothermic peak before the exothermic peak is 20 ℃ or more. Specifically, the temperature difference between the exothermic peak and the endothermic peak before the exothermic peak may be 20 ℃ to 200 ℃.

A Differential Scanning Calorimeter (DSC) means such an apparatus: it can quantitatively measure variables such as change in enthalpy of a sample relative to heat from the position, shape and number of peaks obtained by: the heat flow is expressed as a function of temperature by measuring the amount of energy (enthalpy) required to keep the temperature difference between the sample and the reference material at zero while changing the temperature of the sample and the reference material at a predetermined rate by a program.

In one exemplary embodiment of the present description, the coating composition does not further comprise a p-type doping material.

In one exemplary embodiment of the present description, the coating composition further comprises a p-type doping material.

In this specification, a p-type doped material means a material that gives a host material p-type semiconductor characteristics. The p-type semiconductor characteristics mean characteristics of injecting or transporting holes at the Highest Occupied Molecular Orbital (HOMO) level, that is, characteristics of a material having large hole conductivity.

In one exemplary embodiment of the present specification, as long as the p-type doped material is a material that gives the host material p-type semiconductor characteristics, the material is sufficient, one or two or more kinds thereof may be used, and the type thereof is not limited.

Examples of p-type doping materials are F4TCNQ, or compounds containing boron anions. Specifically, examples of the p-type doping material include any one of the following chemical formulas 9-1 to 9-3 or a fluoroarylborate (Farylborate) -based compound, but are not limited thereto.

[ chemical formula 9-1]

[ chemical formula 9-2]

[ chemical formulas 9-3]

In one exemplary embodiment of the present specification, the content of the p-type doping material is 0 to 50% by weight based on the fluorene-based compound of chemical formula 1.

In one exemplary embodiment of the present specification, the content of the p-type doping material is 0 to 30% by weight based on the total solid content of the coating composition. In one exemplary embodiment of the present specification, it is preferable that the content of the p-type dopant material is 1 to 30% by weight based on the total solid content of the coating composition, and in another exemplary embodiment, it is more preferable that the content of the p-type dopant material is 10 to 30% by weight based on the total solid content of the coating composition.

In an exemplary embodiment of the present specification, the coating composition may further include: a single molecule containing a thermosetting group or a photocurable group; or a single molecule containing an end group capable of forming a polymer by heat.

In an exemplary embodiment of the present specification, a single molecule containing a thermosetting group or a photocurable group, or a single molecule containing a terminal group capable of forming a polymer by heat may be a compound having a molecular weight of 2,000g/mol or less.

In one exemplary embodiment of the present specification, the coating composition further comprises: a single molecule having a molecular weight of 2,000g/mol or less while containing a thermosetting group or a photocurable group; or a single molecule containing an end group capable of forming a polymer by heat.

In one exemplary embodiment of the present specification, the single molecule containing a thermosetting group or a photocurable group is an aryl group such as phenyl, biphenyl, fluorene, and naphthalene; an arylamine; or fluorene, and a single molecule containing a terminal group capable of forming a polymer by heat may mean a single molecule in which a terminal group capable of forming a polymer by heat is substituted.

In one exemplary embodiment of the present specification, the coating composition may further include one or two compounds selected from a polymer compound and a compound in which a thermosetting group or a photocurable group is introduced into a molecule.

In one exemplary embodiment of the present specification, the coating composition may further include a compound in which a thermosetting group or a photocurable group is introduced into a molecule. When the coating composition further includes a compound in which a thermosetting group or a photocurable group is introduced into a molecule, the degree of curing of the coating composition may be further increased.

In an exemplary embodiment of the present specification, the compound in which the thermosetting group or the photocurable group is introduced into the molecule has a molecular weight of 1,000g/mol to 3,000 g/mol.

In an exemplary embodiment of the present specification, the coating composition may further include a polymer compound. When the coating composition further includes a polymer compound, the ink characteristics of the coating composition may be enhanced. That is, the coating composition further comprising a polymer compound may provide a viscosity suitable for coating or inkjet printing.

In one exemplary embodiment of the present specification, the coating composition may further include one or two or more additives selected from a thermal polymerization initiator and a photopolymerization initiator.

In an exemplary embodiment of the present description, the coating composition has a viscosity of 2cP to 15 cP.

In an exemplary embodiment of the present specification, the coating composition has a film retention rate of 95% or more in a film retention test after a heat treatment at 250 ℃ or less. Since the film retention in the film retention test after the heat treatment at 250 ℃ or less is 95% or more, the coating composition of the present invention has excellent resistance to solvents such as toluene and cyclohexanone.

In the film retention test, a film is first formed by spin-coating a coating composition onto a substrate (e.g., glass, etc.), heat-treated in a nitrogen atmosphere, and then the UV absorbance of the film is measured. Thereafter, the film retention was measured by: the film was immersed in a solvent (e.g., toluene and cyclohexanone) for about 10 minutes, the film was dried, and then UV absorbance of the film was measured to compare the sizes of the UV absorbance maximum peaks before and after immersing the film in the solvent (size of UV absorbance maximum peak after immersing the film in the solvent/size of UV absorbance maximum peak before immersing the film in the solvent × 100).

An exemplary embodiment of the present specification provides an organic light emitting device formed by using the coating composition.

An exemplary embodiment of the present specification provides an organic light emitting device including: a first electrode;

a second electrode; and

In the present specification, a cured product means a state in which a photocurable group or a thermosetting group contained in a compound is bonded to another material contained in a layer in which the compound is applied and/or the compound. For example, when the photocurable group or the thermosetting group contains a double bond, this may mean that the double bond becomes a single bond and is converted into a polymerized state between compounds.

In one exemplary embodiment of the present specification, the organic material layer including the coating composition or the cured product thereof is a hole transport layer, a hole injection layer, or a layer that transports and injects holes simultaneously.

In one exemplary embodiment of the present specification, the organic material layer including the coating composition or the cured product thereof is a hole injection layer.

In another exemplary embodiment, the organic material layer including the coating composition or the cured product thereof is a light emitting layer.

In still another exemplary embodiment, the organic material layer including the coating composition or the cured product thereof is a light emitting layer, and the light emitting layer includes a fluorene-based compound as a host of the light emitting layer.

In one exemplary embodiment of the present specification, the organic light emitting device further includes one or two or more layers selected from the group consisting of: a hole injection layer, a hole transport layer, an electron injection layer, an electron blocking layer, and a hole blocking layer.

In one exemplary embodiment of the present description, the first electrode is an anode and the second electrode is a cathode.

According to another exemplary embodiment, the first electrode is a cathode and the second electrode is an anode.

In another exemplary embodiment, the organic light emitting device may be a normal type organic light emitting device in which an anode, an organic material layer having one or more layers, and a cathode are sequentially stacked on a substrate.

In still another exemplary embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a cathode, an organic material layer having one or more layers, and an anode are sequentially stacked on a substrate.

The organic material layer of the organic light emitting device of the present specification may be composed of a single layer structure, but may also be composed of a multilayer structure in which organic material layers having two or more layers are stacked. For example, the organic light emitting device of the present invention may have a structure including two or more layers of a hole injection layer, a hole transport layer, a layer for simultaneously injecting and transporting holes, a light emitting layer, an electron transport layer, an electron injection layer, and a layer for simultaneously injecting and transporting electrons as organic material layers. However, the structure of the organic light emitting device is not limited thereto, and a smaller number of organic layers may be included.

The organic light emitting device of the present specification may be stacked in the order of [ substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron injection layer/electron transport layer/cathode ].

In the organic light emitting device of the present specification according to another exemplary embodiment, [ substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron injection and transport layer/cathode ] may be stacked in this order.

A structure of an organic light emitting device according to an exemplary embodiment of the present specification is illustrated in fig. 1.

Fig. 1 illustrates a structure of an organic light emitting device in which an anode 201, a hole injection layer 301, a hole transport layer 401, a light emitting layer 501, an electron injection and transport layer 601, and a cathode 701 are sequentially stacked on a substrate 101.

However, the structure of the organic light emitting device of the present specification is not limited to fig. 1.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that one or more of the organic material layers are formed using a coating composition including a fluorene-based compound.

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. In this case, the organic light emitting device may be manufactured by: a metal or a metal oxide having conductivity, or an alloy thereof is deposited on a substrate by using a Physical Vapor Deposition (PVD) method such as sputtering or electron beam evaporation to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron injection and transport layer is formed on the anode by a deposition method or a solution method, and then a material that can be used as a cathode is deposited on the organic material layer. In addition to the above-described method, the organic light emitting device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

An exemplary embodiment of the present specification provides a method for manufacturing an organic light emitting device formed by using the coating composition.

Specifically, an exemplary embodiment of the present description includes: preparing a substrate;

forming a first electrode on a substrate;

a second electrode is formed on the organic material layer,

wherein forming an organic material layer includes forming an organic material layer having one or more layers by using the coating composition.

That is, one or more layers of organic material layers are formed by using the coating composition.

In one exemplary embodiment of the present specification, the organic material layer formed by using the coating composition is formed by using a solution method.

In one exemplary embodiment of the present specification, the organic material layer formed by using the coating composition is formed by using spin coating.

In one exemplary embodiment of the present specification, the organic material layer formed by using the coating composition is formed by using a printing method.

Examples of the printing method include inkjet printing, nozzle printing, offset printing, transfer printing, screen printing, or the like, but are not limited thereto.

The coating composition according to one exemplary embodiment of the present specification is suitable for a solution process due to its structural characteristics, so that the organic material layer can be formed by a printing process, and thus has economic benefits in terms of time and cost in manufacturing a device.

In one exemplary embodiment of the present specification, forming an organic material layer formed by using the coating composition includes: coating a cathode or anode with the coating composition; and subjecting the coated coating composition to a heat treatment or a light treatment.

In one exemplary embodiment of the present specification, the heat treatment temperature in the heat treatment of the coating composition is 85 ℃ to 250 ℃.

In another exemplary embodiment, the heat treatment time in the heat treatment of the coating composition may be 1 minute to 1 hour.

In an exemplary embodiment of the present specification, when the coating composition does not include an additive, it is preferable to perform crosslinking by performing heat treatment at a temperature of 100 ℃ to 250 ℃, and more preferably, to perform crosslinking at a temperature of 120 ℃ to 200 ℃.

When forming the organic material layer formed by using the coating composition includes heat-treating or light-treating the coating composition, the plurality of fluorene-based compounds included in the coating composition may form crosslinks, thereby providing the organic material layer including a thin film structure. In this case, when additional layers are stacked on the surface of the organic material layer formed by using the coating composition, the organic material layer may be prevented from being dissolved, morphologically affected, or decomposed by a solvent.

Therefore, when the organic material layer formed by using the coating composition is formed by a method including heat treatment or light treatment of the coated coating composition, resistance to a solvent is increased, so that a plurality of layers can be formed by repeatedly performing a solution deposition method and a crosslinking method, and stability is increased, so that life characteristics of a device can be improved.

For example, even if the coating composition is prepared by using a solvent dissolving the compound and the organic material layer is manufactured by a solution method, the organic material layer may have resistance to the same solvent when cured by heat treatment or light treatment. Therefore, when the organic material layer is formed by using the compound and then the heat treatment process is performed, the solution method may be performed even when an additional organic material layer is applied. As an example, when the coating composition is applied to the hole transport layer during the manufacture of the upper layer (light emitting layer, etc.), the upper layer may also be introduced in a solution method by using a specific solvent to which the cured coating composition exhibits resistance.

In one exemplary embodiment of the present specification, a coating composition including a fluorene-based compound may use a coating composition dispersed by mixing with a polymer binder.

In one exemplary embodiment of the present specification, as the polymer binder, those which do not extremely inhibit charge transport are preferable, and those which do not absorb visible light strongly are preferably used. Examples of the polymer binder include poly (N-vinylcarbazole), polyaniline, and a derivative thereof; polythiophenes and derivatives thereof; poly (p-phenylene vinylene) and derivatives thereof; poly (2, 5-thienylvinylene) and derivatives thereof; a polycarbonate; a polyacrylate; polymethyl acrylate; polymethyl methacrylate; polystyrene; polyvinyl chloride; a polysiloxane; and so on.

In one exemplary embodiment of the present specification, in an organic material layer of an organic light emitting device, the fluorene-based compound may also be included alone, may also be included in a thin film state in which a coating composition including the fluorene-based compound is heat-treated or light-treated, and may also be included as a copolymer in which the fluorene-based compound is mixed with another monomer. Further, the fluorene-based compound may also be included as a copolymer in which the fluorene-based compound is mixed with another polymer, and may also be included as a mixture. In this case, the copolymer in which the fluorene-based compound is mixed with another monomer may be formed by including another monomer in the coating composition, and the copolymer in which the fluorene-based compound is mixed with another polymer may be formed by including another polymer in the coating composition.

In one exemplary embodiment of the present specification, as the anode material, a material having a high work function is generally preferred in order to facilitate hole injection into the organic material layer. Specific examples of the anode material that can be used in the present invention include: metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. ZnO: Al or SnO ₂ Sb; conducting polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polypyrrole and polyaniline; and the like, but are not limited thereto.

As the cathode material, a material having a low work function is generally preferred in order to facilitate electron injection into the organic material layer. Specific examples of the cathode material include: metal, exampleSuch as barium, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; materials of multilayer construction, e.g. LiF/Al or LiO ₂ Al; and the like, but are not limited thereto.

The hole injection layer is a layer that injects holes from the electrode, and the hole injection material is preferably a compound of: which has the ability to transport holes and thus has the effect of injecting holes at the anode and the excellent effect of injecting holes into the light-emitting layer or the light-emitting material, prevents excitons generated from the light-emitting layer from moving to the electron-injecting layer or the electron-injecting material, and is also excellent in the ability to form a thin film. The Highest Occupied Molecular Orbital (HOMO) of the hole injecting material is preferably a value between the work function of the anode material and the HOMO of the adjacent organic material layer. Specific examples of the hole injection material include compounds represented by chemical formula 1, metalloporphyrins, oligothiophenes, arylamine-based organic materials, hexanenitrile-based hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthraquinones, polyaniline-based and polythiophene-based conductive polymers, and the like, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer, and the hole transport material is suitably a material having high hole mobility that can receive holes from the anode or the hole injection layer and transport the holes to the light emitting layer. Examples of the hole transport material include arylamine-based organic materials, conductive polymers, block copolymers having both conjugated and non-conjugated portions, and the like, but are not limited thereto. The hole transport material may specifically be an arylamine based organic material, more specifically a-NPD, but is not limited thereto.

The light emitting material is a material that can receive holes and electrons from the hole transport layer and the electron transport layer, respectively, and combine the holes and the electrons to emit light in the visible light region, and is preferably a material having high quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include: 8-hydroxy-quinoline aluminum complex (Alq) ₃ ) (ii) a A carbazole-based compound; a di-polystyrene based compound; BAlq; 10-hydroxybenzeneA quinoline-metal compound; based on benzene

Oxazole, benzothiazole-based and benzimidazole-based compounds; polymers based on poly (p-phenylene vinylene) (PPV); a spiro compound; a polyfluorene; rubrene; and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. Examples of the host material include a fused aromatic ring derivative or a heterocyclic ring-containing compound and the like. Specifically, examples of the fused aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but examples thereof are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, styryl amine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and examples thereof include pyrene, anthracene, having an arylamino group,

Diindenopyrene, and the like, and styrylamine compounds are compounds in which a substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, and one or two or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamino are substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltrriamine, styryltretramine, and the like. Further, examples of the metal complex include iridium complexes, platinum complexes, and the like, but are not limited thereto.

Specifically, the light emitting layer includes an anthracene derivative as a host, and may include a compound in which a substituted or unsubstituted arylamine is substituted with at least one arylvinyl group as a dopant, but the host and the dopant are not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer, and the electron transport material is suitably a material having high electron mobility that can well receive electrons from the cathode and transport the electrons to the light emitting layer. Specific examples thereof include: al complexes of 8-hydroxyquinoline; comprising Alq ₃ The complex of (1); an organic radical compound; a hydroxyflavone-metal complex; and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials include typical materials with a low work function followed by an aluminum or silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum or silver layer.

The electron injection layer is a layer that injects electrons from the electrode, and the electron injection material is preferably a compound of: it has an ability to transport electrons, has an effect of injecting electrons from a cathode and an excellent effect of injecting electrons into a light emitting layer or a light emitting material, prevents excitons generated from the light emitting layer from moving to a hole injection layer, and is also excellent in an ability to form a thin film. Specific examples thereof include fluorenones, anthraquinone dimethanes, diphenoquinones, thiopyran dioxides, and the like,

Azole,

Oxadiazoles, triazoles, imidazoles, perylene tetracarboxylic acids, fluorenylidene methane, phenanthrolines, anthrones, and the like, and derivatives thereof; a metal complex compound; a nitrogen-containing 5-membered ring derivative; and the like, but are not limited thereto.

Examples of the metal complex compounds include lithium 8-hydroxyquinolyl, zinc bis (8-hydroxyquinoline), copper bis (8-hydroxyquinoline), manganese bis (8-hydroxyquinoline), aluminum tris (2-methyl-8-hydroxyquinoline), gallium tris (8-hydroxyquinoline), bis (10-hydroxybenzo [ h ] quinoline) beryllium, bis (10-hydroxybenzo [ h ] quinoline) zinc, bis (2-methyl-8-quinoline) chlorogallium, bis (2-methyl-8-quinoline) (o-cresol) gallium, bis (2-methyl-8-quinoline) (1-naphthol) aluminum, bis (2-methyl-8-quinoline) (2-naphthol) gallium, and the like, but are not limited thereto.

The electron injection and transport layer is a layer that simultaneously injects and transports electrons. As the electron injection and transport layer material, any material suitable for the electron injection layer and the electron transport layer may be used without limitation. For example, phenanthroline derivatives may be used, but the electron injection and transport layer material is not limited thereto.

The hole blocking layer is a layer that blocks holes from reaching the cathode, and may be generally formed under the same conditions as those of the hole injection layer. Specific examples thereof include

Oxadiazole derivatives or triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, etc., but is not limited thereto.

The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a dual emission type, depending on the material used.

In one exemplary embodiment of the present specification, the fluorene-based compound may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

EMBODIMENTS FOR CARRYING OUT THE INVENTION

Hereinafter, the present specification will be described in detail with reference to examples for specifically describing the present specification. However, the embodiments according to the present specification may be modified into various forms, and should not be construed that the scope of the present specification is limited to the embodiments described below. The embodiments of the present description are provided to more fully describe the present description to those of ordinary skill in the art.

< preparation example >

Synthesis example 1 preparation of Compound 1

(1) Synthesis of intermediate A-1

12.24g (1.3 equiv.) of 1-bromo-4-chloro-2-fluorobenzene, 10g (1.0 equiv.) of 2- (4-chloro-2-fluorophenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan, 0.13g (0.005 equiv.) of PdCl ₂ (AMPHOS) and 8.26g (2.0 equiv.) of Na ₂ CO ₃ Put into a round-bottomed flask and dissolved in 150mL of toluene and 150mL of D ₂ And (4) in O. After raising the temperature to 45 ℃, 1.57g (0.10 eq) of Aliquit336 was injected thereto. After stirring for 12 hours, the reaction was quenched with distilled water, the organic layer was extracted, and then 7.7g of 100% pure intermediate A-1 was obtained with Dichloromethane (DCM) and methanol.

FIG. 2 is a graph showing the results of NMR measurement of intermediate A-1.

(2) Synthesis of intermediate B-1

7.7g (1.0 equivalent) of intermediate A-1, 6.9g (2.2 equivalents) of aniline, 0.75g (0.05 equivalent) of bis (tri-tert-butylphosphino) palladium (0) (Pd) ₂ (t-Bu) P) and 7.14g (2.5 equivalents) of sodium tert-butoxide (Na-t-butoxide) were placed in a round bottom flask and dissolved in 200mL of xylene. After raising the temperature to 130 ℃, the solution was stirred for 12 hours. The reaction was quenched with distilled water, the organic layer was extracted, and then Dichloromethane (DCM) and hexane were used to obtain 8.0g of intermediate B-1 with 96% purity.

(3) Synthesis of Compound 1

After 2g (1.0 equivalent) of intermediate B-1 and 5.36g (2.2 equivalents) of 2-bromo-9- (2, 5-dimethylphenyl) -9- (4-vinylphenyl) -9H-fluorene were placed in a round-bottomed flask and dissolved in 40mL of toluene, 6.48mL (2.5 equivalents) of sodium 2.5M tert-amylate (Na-t-pentoxin) were slowly injected thereto, and then 0.08g (0.02 equivalent) of Pd was introduced thereinto ₂ (t-Bu) P, and the resulting mixture was stirred at 60 ℃ for 6 hours. The reaction was terminated with distilled water, and the organic layer was extracted, followed by THF and ethanol to obtain 1g of compound 1 with 99.7% purity.

Figure 3 shows the HPLC measurement results of compound 1.

In THF: H ₂ HPLC was measured under conditions of O60: 40. By the measured HPLC result, the purity of compound 1 was determined to be 99.7%.

Synthesis example 2 preparation of Compound 2

(1) Synthesis of intermediate A-2

8.0g of 100% pure intermediate A-2 was obtained in the same manner as in (1) of production example 1, except that 1-bromo-4-chlorobenzene was used instead of 1-bromo-4-chloro-2-fluorobenzene in (1) of production example 1.

(2) Synthesis of intermediate B-2

8.0g of 100% pure intermediate B-2 was obtained in the same manner as in (2) of production example 1 except that intermediate A-2 was used instead of intermediate A-1 in (2) of production example 1.

(3) Synthesis of Compound 2

1.0g of Compound 2 with a purity of 99.7% was obtained in the same manner as in (3) of production example 1 except that intermediate B-2 was used instead of intermediate B-1 in (3) of production example 1.

Synthesis example 3 preparation of Compound 3

(1) Synthesis of intermediate B-3

8.0g of 100% pure intermediate B-3 was obtained in the same manner as in (2) of production example 1 except that bromobiphenyl was used in place of the aniline in (2) of production example 1.

(2) Synthesis of Compound 3

1.0g of compound 3 with 99.6% purity was obtained in the same manner as in (3) of production example 1 except that intermediate B-3 was used instead of intermediate B-1 in (3) of production example 1.

Experimental example 1 measurement of film Retention

Coating composition 1 was prepared by dissolving compound 1 prepared in synthesis example 1 and a p-type dopant of the following chemical formula 9-2 in toluene at a concentration of 2 wt% (compound 1: chemical formula 9-2 ═ 8:2 (weight ratio)). Further, coating composition 2 was prepared by dissolving the following comparative compound 1 and the p-type dopant material of the following chemical formula 9-2 in toluene at a concentration of 2 wt% (comparative compound 1: chemical formula 9-2 ═ 8:2 (weight ratio)).

The thin film was formed by spin coating the coating composition 1 and the coating composition 2 on glass, respectively. The film was heat-treated at 220 ℃ for 30 minutes, and UV absorbance was measured. The film was immersed again in toluene for 10 minutes and then dried, and UV absorbance was measured. By comparing the size of the maximum peak of UV absorbance before and after immersion, the film retention can be determined.

[ chemical formula 9-2]

[ comparative Compound 1]

Fig. 4 is a graph showing the results of a film retention experiment for a thin film formed from coating composition 1.

Fig. 5 is a graph showing the results of a film retention experiment for a thin film formed from coating composition 2.

In fig. 4 and 5, the horizontal axis means wavelength and the vertical axis means Optical Density (OD), (a) is a UV measurement immediately after the film is heat-treated (before 10 minutes immersion in toluene), and (b) is a UV measurement after 10 minutes immersion in toluene.

From fig. 4, it can be determined that the film retention rate is 100% in the case of the film formed of the coating composition 1 including the compound represented by chemical formula 1. In contrast, from fig. 5, it can be determined that the film retention rate is 0% in the case of the film formed from the coating composition 2 containing the comparative compound 1 containing no curable group.

Experimental example 2 measurement of energy level

A coating composition in which compound 1 synthesized in synthesis example 1 and comparative compound 2 below were each dissolved in toluene at a concentration of 2 wt% was prepared. The thin film is formed by spin coating the coating composition on the ITO substrate. The energy level of the formed thin film having a thickness of about 30nm was measured by an AC3 apparatus, and the results are shown in table 1 below.

[ comparative Compound 2]

[ Table 1]

	Comparative Compound 2	Compound 1
			HOMO	5.45	5.50
LUMO	2.44	2.40
			Band gap	3.01	3.10

From table 1, it can be confirmed that the HOMO level of compound 1 into which F is introduced tends to be shifted down compared to comparative compound 1 due to the electron-withdrawing effect. Further, compound 1 introduced with F exhibits a larger band gap than comparative compound 1, which brings about a synergistic effect of the triplet state. Therefore, it was confirmed that more smooth hole movement can be formed when compound 1 is applied at the time of manufacturing a device than when comparative compound 1 is applied.

Experimental example 3 production of organic light emitting device

Example 1.

Thinly coated with a thickness of

The glass substrate of Indium Tin Oxide (ITO) of (a) was put in distilled water in which a detergent was dissolved, and ultrasonic washing was performed. In this case, a product manufactured by Fischer co. was used as a cleaning agent, and distilled water filtered twice using a filter manufactured by Millipore co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic washing was repeatedly performed twice for 10 minutes using distilled water.

After completion of the washing with distilled water, the substrate was ultrasonically washed with isopropyl alcohol and acetone solvents and dried, and then the substrate was cleaned for 5 minutes and transferred to a glove box.

A coating composition in which compound 1 and the p-type dopant material of chemical formula 9-2 were dissolved in toluene at a concentration of 1.5 wt% (compound 1: chemical formula 9-2 ═ 8:2 (weight ratio)) was spin-coated on the ITO transparent electrode, and heat-treated (cured) at 220 ℃ for 30 minutes, thereby forming a hole injection layer having a thickness of 30 nm. A toluene solution containing 2 wt% of α -NPD (N, N-di (1-naphthyl) -N, N-diphenyl- (1, 1 '-biphenyl) -4, 4' -diamine) was spin-coated on the hole injection layer formed above, thereby forming a hole transport layer having a thickness of 40 nm. Thereafter, it was transported to a vacuum deposition apparatus, and 9, 1-di-2-naphthyl-Anthracene (ADN) and DPAVBi in a weight ratio (ADN: DPAVBi) of 20: 1 were vacuum deposited on the hole transport layer to have a thickness of 20nm, thereby forming a light emitting layer. BCP was vacuum-deposited on the light emitting layer to have a thickness of 35nm, thereby forming an electron injection and transport layer. LiF and aluminum were sequentially deposited on the electron injecting and transporting layer to have a thickness of 1nm and 100nm, respectively, to form a cathode.

In the above process, the deposition rate of the organic material is maintained at

Per second to

Per second, the deposition rates of lithium fluoride and aluminum of the cathode are respectively kept at

Second and

second, and the degree of vacuum during deposition was maintained at 2X 10 ^-7 Hold in the palm to 5 x 10 ^-6 And (4) supporting.

Example 2.

An organic light-emitting device was manufactured in the same manner as in example 1, except that compound 2 was used instead of compound 1 in example 1.

Example 3.

An organic light-emitting device was manufactured in the same manner as in example 1, except that compound 3 was used instead of compound 1 in example 1.

Comparative example 1.

An organic light-emitting device was fabricated in the same manner as in example 1, except that the following comparative compound 2 was used instead of compound 1 in example 1.

[ comparative Compound 2]

Comparative example 2.

The present inventors tried to form a hole injection layer by using the following comparative compound 1 containing no curable group instead of the compound 1 in example 1, and to form a hole transport layer by spin-coating a toluene solution containing 2 wt% of NPD on the formed hole injection layer, but since the comparative compound 1 was dissolved in the toluene solution containing NPD, a device could not be manufactured.

[ comparative Compound 1]

At 10mA/cm ² The results of measuring the performance of the organic light emitting devices manufactured in examples 1 to 3 and comparative example 1 at the current density of (a) are shown in table 2 below.

[ Table 2]

In table 2, T95 means the time it took for the luminance to decrease from the initial luminance to 95%.

As can be seen from table 2, in the case of the compounds (examples 1 to 3) in which F was introduced, the devices could be driven even at low voltage, meaning that the compounds had improved mobility compared to comparative compound 2 due to the introduction of F. Further, it was confirmed that the service lives of examples 1 to 3 were improved as compared with the service life of comparative example 1.

Claims

1. A fluorene-based compound represented by the following chemical formula 1:

[ chemical formula 1]

In the chemical formula 1, the first and second,

m1 and m2 are each an integer of 1 to 4,

n1 and n6 are each independently an integer from 0 to 5,

n2 and n5 are each independently an integer from 0 to 4,

n3 and n4 are each independently an integer of 0 to 3, an

2. The fluorene-based compound of claim 1, wherein the photocurable group or the thermosetting group is any one of the following structures:

3. the fluorene-based compound according to claim 1, wherein R1 to R6 are the same as or different from each other, and are each independently hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

4. The fluorene-based compound according to claim 1, wherein Ar1 and Ar2 are the same as or different from each other, and each is independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

5. The fluorene-based compound according to claim 1, wherein X3 and X4 are the same as or different from each other, and each is independently a photocurable group or a thermosetting group.

6. The fluorene-based compound according to claim 1, wherein chemical formula 1 is represented by the following chemical formula 1-1:

[ chemical formula 1-1]

In the chemical formula 1-1,

x1 to X4, L1, L2, R1 to R6, Ar1, Ar2, and n1 to n6 are the same as those defined in chemical formula 1.

7. The fluorene-based compound according to claim 1, wherein chemical formula 1 is any one of the following structures:

8. a coating composition comprising the fluorene-based compound according to any one of claims 1 to 7.

9. The coating composition of claim 8, further comprising a p-type doping material.

10. The coating composition of claim 9, wherein the p-type doping material is F4TCNQ, or a boron anion containing compound.

11. The coating composition of claim 8, further comprising: a single molecule containing a thermosetting group or a photocurable group; or a single molecule containing an end group capable of forming a polymer by heat.

12. An organic light emitting device comprising:

a first electrode;

a second electrode; and

wherein one or more of the organic material layers comprise the coating composition according to claim 8 or a cured product thereof, and

13. The organic light-emitting device according to claim 12, wherein the organic material layer comprising the coating composition or a cured product thereof is a hole-transporting layer, a hole-injecting layer, or a layer that transports and injects holes simultaneously.

14. A method of fabricating an organic light emitting device, the method comprising:

preparing a substrate;

forming a first electrode on the substrate;

forming a second electrode on the organic material layer,

wherein forming the organic material layer comprises forming an organic material layer having one or more layers by using the coating composition according to claim 8.

15. The method of claim 14, wherein forming the organic material layer by using the coating composition comprises:

coating the coating composition on the first electrode; and

the coated coating composition is subjected to a heat treatment or a light treatment.